Hydration of olefines



Patented Aug. 25 i936 untrue STATES ?A'EENT @FFEQE HYDRATION OF OLEFINES Sutton, England No Drawing. Application October 4, 1933, Serial No 692,220. In Great Britain October 18, 1932 12 Claims.

The present invention relates to the production of secondary and/or tertiary butyl alcohols from butene 1 and 2 and/or iso-butylene by the direct combination of the respective olefine or olefines with water vapor. According to this invention the respective olefine or olefines and water vapor are caused to combine at high temperatures at atmospheric or increased pressures in the presence of a solid catalyst compounded from phosphoric acid with one or more of the following metals; manganese, copper, iron, cobalt or uranium or the oxides or other compounds thereof, the amount of phosphoric acid present in the catalyst being in excess of that required to form the orthophosphate of the selected metal or metals.

In addition to one or more of the metals it is advantageous toincorporate boron, the amount of phosphoric acid used in that event being in excess of that required to form the orthophosphate of boron as well as the orthophosphate of the metal or metals.

The catalyst may be used in the solid state in the form of granules, flakes and so forth or may be supported on inert carriers such as electrode carbon and the like, or these materials may be impregnated with the catalyst in liquid form, and subsequently dried. The reaction may be car ried out at temperatures of 100-300 C. At mospheric pressure may be employed or increased pressures up to 100 atmospheres.

The following examples illustrate the manner in which the invention may be carried into effect and the nature of the results obtained:

Example- I A catalyst was prepared consisting of 2.6 molecules of phosphoric acid, one moleculeof manganese oxide, and half a molecule of boric anhydride. Over 100 cc. of this catalyst, at a temperature of 240 C. butylene (a mixture of butene 1 and 2) mixed with steam in the molar proportions of 6.1 molecules butylene to 3.9 molecules steam was passed at a rate of 440 litres per hour (calculated at normal temperature and pressure) under a total pressure of 10 atmospheres. The hourly output of secondary butyl alcohol was 2.53 grams. The butyl alcohol was obtained in the form of a 1.2% condensate. A certain amount of methyl ethyl ketone was also formed.

Example II Over the same amount of the same catalyst as in Example I, and at a temperature of 230 C. butylene mixed with steam in the molar propor- (Cl. 260l56) tions of 3.85 molecules butylene to 4.15 molecules of steam was passed at a rate of 220 litres per hour (calculated at normal temperature and pressure) under a total pressure of 8 atmospheres. The hourly output of secondary butyl alcohol was .1 2.09 grams. The butyl alcohol was obtained in the form of a 1.13% condensate. A certain amount of methyl ethyl ketone was also formed.

It iso-butylene is used in Example I or II in place of butylene under the same conditions, ter- 10 tiary alcohol is formed.

What we claim is:-

1. The method. of converting butylic olefines and Water vapor direct into the corresponding a1- cohols, comprising subjecting a mixture of the hi butylic olefine and Water vapor to the action of an elevated temperature in the presence of a solid catalyst comprising essentially phosphoric acid and the phosphate of a metal taken from a group consisting of manganese, copper, iron, cobalt, uranium, the amount of phosphoric acid present in the catalyst being in excess of that required to form the orthophosphate of the metal or metals selected.

2. The method of converting butylic olefines 25 and water vapor direct into the corresponding alcohols comprising subjecting a mixture of the butylic olefine and Water vapor tothe action of a temperature ranging from 100 C. to 300 C. in the presence of a solid catalyst comprising essentially phosphoric acid and the phosphate of a metal taken from a group consisting of manganese, copper, iron, cobalt, uranium, the amount of phosphoric acid present in the catalyst being in excess of that required to form the orthophosphate of the metal or metals selected.

3. The method of converting butylic olefines and Water vapor direct into the corresponding alcohols, comprising subjecting a mixture of the butylic olefine and water vapor to the action of a temperature ranging from 100 C. to 300 C. and an elevated pressure not exceeding 100 atmospheres in the presence of a solid catalyst comprising essentially phosphoric acid and the phosphate of a metal taken from a group consisting of manganese, copper, iron, cobalt, uranium, the amount of phosphoric acid present in the catalyst being in excess of that required to form the orthophosphate of the metal or metals selected.

4. The method of producing tertiary butyl alecho] direct from iso-butylene and water vapor, comprising subjecting a mixture of the isobutylene and water vapor to the action of an elevated temperature in the presence of a solid catalyst comprising essentially phosphoric acid and the phosphate of a metal taken from a group consisting of manganese, copper, iron, cobalt, uranium, the amount of phosphoric acid present in the catalyst being in excess of that required to form the orthophosphate of the metal or metals selected.

5. The method of producing tertiary butyl alcohol direct from iso-butylene and Water vapor, comprising subjecting a mixture of the isobutylene and Water vapor to the action of a temperature ranging from 100 C. to 300 C. in the presence of a solid catalyst comprising essentially phosphoric acid and the phosphate of a metal taken from a group consisting of manganese, copper, iron, cobalt, uranium, the amount of phosphoric acid present in the catalyst being in excess of that required to form the orthophosphate of the metal or metals selected.

6. The method of producing tertiary butyl alcohol direct from iso-butylene and Water vapor, comprising subjecting a mixture of the iso-butylene and water vapor to the action of a temperature ranging from 100 C. to 300 C. and an elevated pressure not exceeding 100 atmospheres in the presence of a solid catalyst comprising essentially phosphoric acid and the phosphate of a metal taken from a group consisting of manganese, copper, iron, cobalt, uranium, the amount of phosphoric acid present in the catalyst being in excess of that required to form the orthophosphate of the metal or metals selected.

7. The method of producing secondary butyl alcohol direct from butylene and water vapor, comprising subjecting a, mixture of the butylene and water vapor to the action of an elevated temperature in the presence of a solid catalyst comprising essentially phosphoric acid and. the phosphate of a metal taken from a group consisting of manganese, copper, iron, cobalt, uranium, the amount of phosphoric acid present in the catalyst being in excess of that required to form the vortho-phosphate of the metal or metals selected.

8. The method of producing secondary butyl alcohol direct from butylene and Water vapor, comprising subjecting a mixture of the butylene and Water vapor to the action of a temperature ranging from 100 C. to 800 C. in the presence of a solid catalyst comprising essentially phosphoric acid and the phosphate of a metal taken from a group consisting of manganese, copper, iron, cobalt, uranium, the amount of phosphoric acid present in the catalyst being in excess of that required to form the orthophosphate of the metal or metals selected.

9. The method of producing secondary butyl alcohol direct from butylene and water vapor, comprising subjecting a mixture of the butylene and water vapor to the action of a temperature ranging from 100 C. to 300 C. and an elevated pressure not exceeding 100 atmospheres in the presence of a solid catalyst comprising essentially phosphoric acid and the phosphate of a metal taken from a group consisting of manganese, copper, iron, cobalt, uranium, the amount of phosphoric acid present in the catalyst being in excess of that required to form the orthophosphate of the metal or metals selected.

10. The method of converting butylic olefines and water vapor direct into the corresponding alcohols, comprising subjecting a mixture of the butylic olefine and Water vapor to the action of an elevated temperature in the presence of a solid catalyst comprising essentially phosphoric acid and the phosphate of a metal taken from a group consisting of manganese, copper, iron, cobalt, uranium, together with the phosphate of boron, the amount of phosphoric acid present in the catalyst being in excess of that required to form the orthcphosphates of boron and of the metal or metals selected.

11. The method of converting butylic olefines and Water vapor direct into the corresponding alcohols comprising subjecting a mixture of the butylic olefine and water vapor to the action of an elevated temperature in the presence of a solid catalyst comprising essentially phosphoric acid and the phosphate of manganese, the amount of phosphoric acid present in the catalyst being in excess of that required to form the orthophosphate of manganese.

12. The method of converting butylic olefines and Water vapor direct into the corresponding alcohols comprising subjecting a mixture of the butylic olefine and water vapor to the action of an elevated temperature in the presence of a solid catalyst comprising essentially phosphoric acid and the phosphate of copper, the amount of phosphoric acid present in the catalyst being in excess of that required to form the orthophosphate of copper.

WALTER PHILIP JOSHUA. HERBERT MUGGLETON STANLEY. JOHN BLAIR DY MOCK. 

